System and Method For PH Control Of Lean MEG Product From MEG Regeneration and Reclamation Packages

ABSTRACT

A lean MEG stream having a first pH level is contacted with a CO 2 -rich gas stream to yield a lean MEG product having a second different and lower pH level preferably in a range of 6.5 to 7.0. The system and method can be readily incorporated into a slipstream MEG recovery package, with a source of the lean MEG stream being a MEG regeneration section of the package. The CO 2 -rich gas could be a vented CO 2  stream from the MEG reclamation section of the package. Unlike hydrochloric and acetic acid overdosing, CO 2  overdosing of the lean MEG stream does not lead to rapid acidification of the lean MEG product to be stored or injected.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application which claims priority to U.S. patent application Ser. No. 14/500,295 filed on Sep. 29, 2014, which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

Slipstream MEG recovery packages use a regeneration section to remove water from an incoming rich MEG feed stream and produce a lean MEG stream. A portion of this lean MEG stream is routed to a reclamation unit or section where the salt component is removed to yield a salt-free, pH neutral, lean MEG stream. This salt-free lean MEG stream is then blended with the remaining lean MEG stream to produce a lean MEG product having up to 3 wt % dissolved salts and available for re-injection into the gas production line as hydrate inhibitor.

For gas fields where significant quantities of calcium and other divalent cations are present in the formation water, a calcium removal unit or section is located upstream of the regeneration section. The calcium is removed from the rich MEG stream by elevating the pH through the addition of sodium or potassium carbonates, hydroxides, or some combination thereof. The lean MEG exits the calcium removal section with an elevated pH, typically above 9.5.

Because carbonate and hydroxide are often added in excess of the required stoichiometric quantity, un-reacted carbonate and hydroxide is carried through the regeneration system and into the lean MEG product. Removal of water from the rich MEG in the regeneration section further elevates the pH of the lean MEG product sent for re injection to above 10. Mixing this high pH lean MEG with the calcium-rich formation water in the gas production pipeline can lead to increased scaling of the pipeline by precipitation of, for example, calcium carbonate.

Therefore, a need exists to reduce the pH of the lean MEG product prior to injection and, in turn, mitigate pipeline scaling. Acidification of the lean MEG with hydrochloric acid (HCl) is an option but overdosing with hydrochloric acid can lead to rapid reduction in pH to levels at which corrosion of carbon steel pipework and vessels may occur.

SUMMARY OF THE INVENTION

A lean MEG stream having a first pH level (e.g., pH>9.5) is contacted with a CO₂-rich gas stream to yield a lean MEG product having a second different pH level preferably in a range of 6.5 to 7.0. The CO₂-rich gas could be a vented CO₂ stream from a MEG reclamation unit.

Carbon dioxide is preferred to hydrochloric acid (HCl) and acetic acid (CH₃CO₂H) for pH control because overdosing with CO₂—i.e., adding it in excess of the required stoichiometric quantity—does not lead to the significant reduction in pH observed with hydrochloric acid or the accumulation of acetates observed with acetic acid.

Objectives of this invention include providing a system and method that reduces the pH of lean MEG product prior to injection, mitigates the potential for pipeline scaling, does not make use of dosing with organic or inorganic acids to control the pH of the lean MEG product, is less sensitive to overdosing conditions than those organic and inorganic acids, and does not cause rapid reduction in pH levels when an overdose condition occurs.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of a preferred embodiment of a system and method of this invention. A vessel located downstream of a MEG regeneration section receives a high pH lean MEG stream and allows the steam to come into contact with a CO₂-rich gas.

FIG. 2 is a graph illustrating a lean MEG stream with alkalinity present as sodium carbonate as the stream is treated with CO₂, acetic acid, and hydrochloric acid.

FIG. 3 is a graph illustrating a lean MEG stream with alkalinity present as sodium hydroxide as the stream is treated with CO₂, acetic acid, and hydrochloric acid.

ELEMENTS AND NUMBERING USED IN THE DRAWINGS

10 Vessel

15 Rich MEG steam

20 Lean MEG stream

21 Portion of lean MEG stream 20

30 MEG regeneration unit or section

40 CO₂-rich gas 40

50 Lean MEG product exiting 10

60 MEG reclamation unit or section

61 Salt-free lean MEG stream

70 Calcium removal unit or section

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring to FIG. 1, a preferred embodiment of a system and method for adjusting a pH level of a lean MEG steam includes a vessel 10 which receives a lean MEG stream 20 from a lean MEG source such as a regeneration unit or section 30 of a slipstream MEG recovery package. Typically, stream 20 has a pH level above 9.5, as does rich MEG stream 15 upstream of the regeneration section 30. Within vessel 10, this high pH lean MEG stream 20 comes into contact with a CO₂-rich gas 40 (i.e., greater than 50% CO₂ content). Vessel 10 can be a contactor vessel of a kind known in the art.

The CO₂ in gas 40 forms acidic solutions when dissolved in the MEG-water mixture of stream 20, thereby reducing the pH. A lean MEG product 50 having a second lower pH exits the vessel 10. Preferably, product 50 has a pH level in a range of 6.5 to 7. No inorganic acids such as HCl or organic acids such as acetic or citric acid is required for reducing the pH to this level.

The CO₂-rich gas 40 can be from any source preferable but is more preferably a vent stream from a reclamation unit or section 60 of the slipstream MEG recovery package. Similar to MEG regeneration section 30, MEG reclamation section 60 is of a kind well-known in the art.

A salt-free lean MEG stream 61 which exits the reclamation section 60 can be mixed with the lean MEG stream 20 prior to stream 20 entering vessel 10. Additionally, a portion 21 of the lean MEG stream 20 which exits the regeneration section 30 can be routed to the reclamation unit 60.

In slipstream MEG recovery packages that make use of a calcium removal unit or section 70 upstream of the regeneration unit 30, excess carbonate that finds its way into the reclamation section 60 degrades to form CO₂ (and hydroxide) under the elevated temperature, low pressure regime of a flash separator (not shown).

Referring to FIGS. 2 and 3, unlike hydrochloric and acetic acid overdosing, CO₂ overdosing within vessel 10 does not lead to rapid acidification of the lean MEG product 50. In a CO₂ overdosing condition, the pH level remains above 6 whereas in an acetic acid and hydrochloric acid overdosing condition the pH level falls below 4 and 2 respectively. Therefore, the system and method of this invention is less sensitive to overdosing conditions than prior art methods.

As mentioned above, acidification with CO₂ removes the risk which occurs with inorganic acids (HCl) and the absence of carboxylates (acetate), namely, overdosing to the point of potentially damaging pH levels. In addition, carboxylates are highly soluble in MEG and are difficult to remove once added to the MEG system. The accumulation of carboxylates can lead to operational problems as the density and viscosity of the MEG increases with increasing carboxylate content. Hydrochloric acid converts readily to salt plus water; carbon dioxide converts to bicarbonate which is much more easily managed in the MEG system than carboxylates. Although the CO₂ reduces the pH, the ‘alkalinity’ (OH— plus HCO₃— plus CO₂) is not reduced.

To examine the “scaling” potential for the system and method, the following software simulation was run employing OLI Analyzer v 9.1.5 (OLI Systems, Inc., Cedar Knolls, N.J.).

Starting solution: 90 wt % MEG (on salt-free basis) at 40° C. containing 30,000 mg/kg_(solvent) sodium chloride, 250 mg/kg_(solvent) of sodium carbonate and 25 mg/kg_(solvent) of sodium hydroxide. The pH of this mixture was 10.053 or about 10 (see Table 1, col. A, below).

Acidification: The MEG solution was neutralized to pH=7.0 and to pH=6.5 using HCl acetic acid and CO₂. Quantities of HCl, CH₃CO₂H and CO₂ added are shown in Table 1, rows 12-14, below.

Scaling Test: Scaling potential of the acidified solutions was determined by adding in separate simulations MgCl₂, CaCl₂, FeCl₂, SrCl₂ and BaCl₂ to the lean MEG solutions at the quantities shown in Table 1, rows 19-23.

TABLE 1 Software Simulation of Scaling Potential. 1 A B C D E F G 2 3 TEMP 40 40 40 40 40 40 40 4 5 H2O g 100,000 100,000 100,000 100,000 100,000 100,000 100,000 6 MEG g 900,000 900,000 900,000 900,000 900,000 900,000 900,000 7 NaCl g 30,000 30,000 30,000 30,000 30,000 30,000 30,000 8 Na2CO3 g 250 250 250 250 250 250 250 9 NaOH g 25 25 25 25 25 25 25 10 11 ACIDIFICATION 12 HCl g 0 136 — — 160 — — 13 CHCO2H g 0 — 228 — — 279 — 14 CO₂ g 0 — — 239 — — 478 15 16 pH — 10.05 7.01 7.01 7.01 6.50 6.50 6.50 17 18 SCALING TEST POST ACIDIFICATION 19 MgCl2 for Mg g precipitation as Mg(OH)2 20 CaCl2 for Ca g 1.4 840 880 250 4300 5300 800 precipitation as CaCO3 21 FeCl2 for Fe g 0.1 1.5 1.7 0.8 6.7 7.7 2.4 precipitation as FeCO3 22 SrCl2 for Sr g 0.5 650 660 200 3900 3950 620 precipitation as SrCO3 23 BaCl2 for Ba g 0.2 7 13.7 2.1 35 80 6.3 precipitation as BaCO3

Results: For the starting solution (col. A, pH=10.0) precipitation of divalent cations as carbonate occurs on addition of 1.4 g of CaCl₂. After acidification to pH 7.0 with HCl, the quantity of calcium chloride added before precipitation of CaCO₃ increases to 840 g from 1.4 g. The effect with acetic acid is similar with precipitation starting at 880 g of CaCl₂. The equivalent scaling point with carbon dioxide occurs at 250 g, less than that for HCl or acetic acid but a considerable improvement on the 1.4 g for the untreated sample.

Similar trends are observed for the other divalent cations (Fe, Sr, Ba) although some are more insoluble than others. Iron, in particular, tends to precipitate out readily. At pH=6.5 (col. E-G) the trends agree with those shown at pH=7.0 (col. B-D), i.e. precipitation of divalent cations (Ca, Fe, Sr, and Ba) from the lean MEG is inhibited by addition of CO₂ to the alkaline lean MEG mixture.

While preferred embodiments have been described, the invention is defined by the following claims and their full range of equivalency. 

What is claimed:
 1. A system for adjusting a pH level of a MEG stream, the system comprising: a vessel having an inlet to receive a MEG stream and ported to receive a CO₂-rich gas, the MEG stream and CO₂-rich gas coming into contact with one another within the vessel.
 2. A system according to claim 1, the MEG stream having a first pH level when entering the vessel and, after coming into contact with the CO₂-rich gas, having a second different pH level when exiting the vessel.
 3. A system according to claim 2 wherein an amount of the CO₂-rich gas is at least equal to a stoichiometric quantity effective for achieving a desired second lower pH level.
 4. A system according to claim 3 wherein the amount of CO₂-rich gas exceeds the stoichiometric quantity.
 5. A system according to claim 2 wherein the second different pH level is at least
 6. 6. A system according to claim 2 wherein the second different pH level is
 7. 7. A system according to claim 1 further comprising a source of the CO₂-rich gas is a vented CO₂ stream from a MEG reclamation unit.
 8. A system according to claim 1 wherein the MEG stream is mixed with a second MEG stream having a different pH level than a pH level of the MEG stream.
 9. A system according to claim 8 further comprising a source of the second MEG stream is a MEG reclamation unit.
 10. A system according to claim 8 wherein the second MEG stream has a pH level of
 7. 11. A system according to claim 1 further comprising a source of the MEG stream is a MEG regeneration unit.
 12. A system according to claim 11 wherein a portion of the MEG stream exiting the regeneration unit is routed to a reclamation unit. 